The use of high pressure fossil derived hydrogen limits the commercial prospects of transforming sorbitol to glycols. Ni-Re/C catalyst which was developed in this study demonstrated high selectivity toward hydrogenative cleavage of C2-C3 and C3-C4 bonds of sorbitol to produce glycols under 1 MPa nitrogen. Acetol which is proposed as important intermediate to explain the reaction mechanism was first detected in the sorbitol conversion reactions. Detailed investigations showed that the presence of Re could prevent the sintering of Ni particles during the reduction process and make the catalyst efficiently generate hydrogen on the active sites to selectively cleave C-C bonds in sorbitol under nitrogen atmosphere. (C) 2014 Elsevier B.V. All rights reserved.